This invention is generally directed to developer compositions, and more specifically, the present invention relates to developer compositions with coated carrier particles. In one embodiment of the present invention, the carrier particles are comprised of a semiconductive or conductive core, such as a ferrite core, with coating thereover generated from a mixture of polymers that are not in close proximity thereto in the triboelectric series. In another aspect of the present invention, the carrier particles are prepared by a dry coating process wherein a mixture of certain polymers are applied to the carrier enabling relatively constant conductivity parameters; and also wherein the triboelectric charge on the carrier can vary, sometimes significantly, depending on the coatings selected. The developer compositions of the present invention can be selected for electrostatographic or electrophotographic imaging systems, especially xerographic imaging and printing processes. Developer compositions comprised of the coated semiconductive ferrite carrier particles illustrated herein are useful in imaging methods wherein relatively constant conductivity parameters may be desired. In the aforementioned imaging processes, the triboelectric charge on the carrier particles can be preselected in embodiments of the present invention depending, for example, on the polymer composition applied to the carrier core.
The electrostatographic process, and particularly the xerographic process, is well known. This process involves the formation of an electrostatic latent image on a photoreceptor, followed by development, and subsequent transfer of the image to a suitable substrate. Numerous different types of xerographic imaging processes are known wherein, for example, insulative toner particles or conductive toner compositions are selected depending on the development systems used. Moreover, of value with respect to the aforementioned developer compositions is the appropriate triboelectric charging values associated therewith, as it is these values that can enable continued constant developed images of high quality and excellent resolution.
Carrier particles for use in the development of electrostatic latent images are described in many patents including, for example, U.S. Pat. No. 3,590,000. These carrier particles may be comprised of various cores, including steel, with a coating thereover of fluoropolymers, and terpolymers of styrene, methacrylate, and silane compounds. Several efforts have focused on the attainment of coatings for carrier particles for the purpose of improving development quality, and also to permit particles that can be recycled, and that do not adversely effect the imaging member in any substantial manner. Many of the present commercial coatings can deteriorate rapidly, especially when selected for a continuous xerographic process where the entire coating may separate from the carrier core in the form of chips or flakes, and fail upon impact or abrasive contact with machine parts and other carrier particles. These flakes or chips, which cannot generally be reclaimed from the developer mixture, can have an adverse effect on the triboelectric charging characteristics of the carrier particles thereby providing images with lower resolution in comparison to those compositions wherein the carrier coatings are retained on the surface of the core substrate. Further, another problem encountered with some prior art carrier coatings resides in fluctuating triboelectric charging characteristics, particularly with changes in relative humidity. The aforementioned modification in triboelectric charging characteristics can result in developed images of lower quality, and with background deposits.
There is illustrated in U.S. Pat. No. 4,233,387, the disclosure of which is totally incorporated herein by reference, coated carrier components for electrostatographic developer mixtures comprised of finely divided toner particles clinging to the surface of the carrier particles. Specifically, there is disclosed in this patent coated carrier particles obtained by mixing carrier core particles of an average diameter of from between about 30 microns to about 1,000 microns with from about 0.05 percent to about 3.0 percent by weight, based on the weight of the coated carrier particles, of thermoplastic resin particles. The resulting mixture can then be dry blended until the thermoplastic resin particles adhere to the carrier core by mechanical impaction and/or electrostatic attraction. Thereafter, the mixture can be heated to a temperature of from about 320.degree. F. to about 650.degree. F. for a period of 20 minutes to about 120 minutes enabling the thermoplastic resin particles to melt and fuse on the carrier core. While the developer and carrier particles prepared in accordance with the process of this patent, the disclosure of which is totally incorporated herein by reference, are suitable for their intended purposes, the conductivity values of the resulting particles may not be constant in all instances, for example when a change in carrier coating weight is accomplished to achieve a modification of the triboelectric charging characteristics; and further with regard to the '387 patent, in some situations carrier and developer mixtures with only specific triboelectric charging values can be generated when certain conductivity values or characteristics are contemplated. With the invention of the present application, the conductivity of the resulting carrier particles is substantially constant, and moreover the triboelectric values can be selected to vary significantly, for example, from less than -15 microcoulombs per gram to greater than -70 microcoulombs per gram depending on the polymer mixture selected for affecting the coating process.
Ferrite carrier cores are known, reference for example U.S. Pat. No. 4,485,162, the disclosure of which is totally incorporated herein by reference, which patent illustrates magnetic carrier powders comprising particles of a ferrite of the formula as recited, for example, in Claim 1, wherein x is greater than 53 molar percent, and wherein each carrier is capable of exhibiting a changeable resistance of from about 10.sup.14 ohms when 100 volts are applied, and the ferrites are free of a resin coating. Ferrite carriers are also disclosed in U.S. Pat. Nos. 2,846,333; 2,452,529; 3,929,657 and 4,125,667, the disclosures of each of these patents being totally incorporated herein by reference.
Other patents include U.S. Pat. No. 3,939,086, which teaches steel carrier beads with polyethylene coatings, see column 6; U.S. Pat. No. 4,264,697, which discloses dry coating and fusing processes; 3,533,835; 3,658,500; 3,798,167; 3,918,968; 3,922,382; 4,238,558; 4,310,611; 4,397,935 and 4,434,220.
With further reference to the prior art, carriers obtained by applying insulating resinous coatings to porous metallic carrier cores using solution coating techniques may be undesirable in some situations from a number of viewpoints. For example, the coating material can usually reside in the pores of the carrier cores, rather than at the surfaces thereof, and therefore may not be available for triboelectric charging when the coated carrier particles are mixed with finely divided toner particles. Attempts to resolve this problem by increasing the carrier coating weights, for example, to as much as 3 percent or greater to provide an effective triboelectric coating to the carrier particles can involve the processing of excessive quantities of solvents, and further usually these processes can result in low product yields. Also, solution coated carrier particles, when combined and mixed with finely divided toner particles, provide in some instances triboelectric charging values which may be too low for many uses. The powder coating process illustrated herein eliminates or minimizes these disadvantages, and further there results carriers that enable developer mixtures that are capable of generating high and useful triboelectric charging values with finely divided toner particles, and also wherein the carrier particles are of a substantially constant conductivity range, or wherein the conductivity may be preselected. Additionally, there can be achieved with the present invention, independent of one another, desirable triboelectric charging characteristics and conductivity values; that is, for example, the triboelectric charging parameter is not dependent or confined to the carrier coating weight as is believed to be the situation with the process of U.S. Pat. No. 4,233,387 wherein an increase in coating weight on the carrier particles may function to also permit an increase in the triboelectric charging characteristics. With the carrier compositions of the present invention, in embodiments thereof there can be formulated conductive developers with selected triboelectric charging characteristics and/or conductivity values in a number of different combinations.
Thus, for example, there can be formulated in accordance with the invention of the present application developers with conductivities of from about 10.sup.-5 mho (cm).sup.1 to about 10.sup.-17 mho (cm).sup.-1 as determined in a magnetic brush conducting cell, and triboelectric charging values of from about a -8 to about a -80 microcoulombs per gram on the carrier particles as determined by the known Faraday Cage technique. The developers of the present invention can be formulated with constant conductivity values and different triboelectric charging characteristics by, for example, maintaining the same coating weight on the carrier particles and changing the polymer coating ratios. Similarly, there can be formulated developer compositions wherein constant triboelectric charging values are achieved and the conductivities are altered by retaining the polymer ratio coating constant and modifying the coating weight for the carrier particles.
In U.S. Pat. Nos. 4,935,326 and 4,937,166, the disclosures of which are totally incorporated herein by reference, there are illustrated developers with carrier cores, including ferrites in general, which cores can be coated with a polymer mixture wherein the polymers are not in close proximity in the triboelectric series.